Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments
Abstract
In methanol-to-hydrocarbon chemistry, methanol and dimethyl ether (DME) can act as methylating agents. Therefore, in this paper we focus on the different reactivity of methanol and DME towards benzene methylation in H-ZSM-5 at operating conditions by combining first principles microkinetic modeling and experiments. Methylation reactions are known to follow either a concerted reaction path or a stepwise mechanism going through a framework-bound methoxide. By constructing a DFT based microkinetic model including the concerted and stepwise reactions, product formation rates can be calculated at conditions that closely mimic the experimentally applied conditions. Trends in measured rates are relatively well reproduced by our DFT based microkinetic model. We find that benzene methylation with DME is faster than with methanol but the difference decreases with increasing temperature. At low temperatures, the concerted mechanism dominates, however at higher temperatures and low pressures the mechanism shifts to the stepwise pathway. This transition occurs at lower temperatures for methanol than for DME, resulting in smaller reactivity differences between methanol and DME at high temperature. Finally, our theory-experiment approach shows that the widely assumed rate law with zeroth and first order in oxygenate and hydrocarbon partial pressure is not generally applicable and depends on the applied temperature,more »
- Authors:
-
[1];
- SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). Dept. of Chemical Engineering; Ghent Univ. (Belgium). Center for Molecular Modeling
- Univ. of Oslo (Norway). Centre for Materials Science and Nanotechnology. Dept. of Chemistry; Haldor Topsøe A/S, Kongens Lyngby (Denmark)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). Dept. of Chemical Engineering
- Univ. of Oslo (Norway). Centre for Materials Science and Nanotechnology. Dept. of Chemistry
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Ghent Univ. (Belgium); Univ. of Oslo (Norway)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Belgian American Educational Foundation (BAEF); Research Foundation - Flanders (FWO) (Belgium); European Union (EU)
- OSTI Identifier:
- 1461966
- Alternate Identifier(s):
- OSTI ID: 1591661
- Grant/Contract Number:
- AC02-76SF00515; 606965
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Today
- Additional Journal Information:
- Journal Volume: 312; Journal ID: ISSN 0920-5861
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zeolites; methanol-to-hydrocarbons; microkinetic modeling; methylation; methanol; dimethyl ether
Citation Formats
De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, and Bligaard, Thomas. Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments. United States: N. p., 2018.
Web. doi:10.1016/j.cattod.2018.02.042.
De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, & Bligaard, Thomas. Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments. United States. https://doi.org/10.1016/j.cattod.2018.02.042
De Wispelaere, Kristof, Martinez-Espin, Juan S., Hoffmann, Max J., Svelle, Stian, Olsbye, Unni, and Bligaard, Thomas. Sat .
"Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments". United States. https://doi.org/10.1016/j.cattod.2018.02.042. https://www.osti.gov/servlets/purl/1461966.
@article{osti_1461966,
title = {Understanding zeolite-catalyzed benzene methylation reactions by methanol and dimethyl ether at operating conditions from first principle microkinetic modeling and experiments},
author = {De Wispelaere, Kristof and Martinez-Espin, Juan S. and Hoffmann, Max J. and Svelle, Stian and Olsbye, Unni and Bligaard, Thomas},
abstractNote = {In methanol-to-hydrocarbon chemistry, methanol and dimethyl ether (DME) can act as methylating agents. Therefore, in this paper we focus on the different reactivity of methanol and DME towards benzene methylation in H-ZSM-5 at operating conditions by combining first principles microkinetic modeling and experiments. Methylation reactions are known to follow either a concerted reaction path or a stepwise mechanism going through a framework-bound methoxide. By constructing a DFT based microkinetic model including the concerted and stepwise reactions, product formation rates can be calculated at conditions that closely mimic the experimentally applied conditions. Trends in measured rates are relatively well reproduced by our DFT based microkinetic model. We find that benzene methylation with DME is faster than with methanol but the difference decreases with increasing temperature. At low temperatures, the concerted mechanism dominates, however at higher temperatures and low pressures the mechanism shifts to the stepwise pathway. This transition occurs at lower temperatures for methanol than for DME, resulting in smaller reactivity differences between methanol and DME at high temperature. Finally, our theory-experiment approach shows that the widely assumed rate law with zeroth and first order in oxygenate and hydrocarbon partial pressure is not generally applicable and depends on the applied temperature, pressure and feed composition.},
doi = {10.1016/j.cattod.2018.02.042},
journal = {Catalysis Today},
number = ,
volume = 312,
place = {United States},
year = {Sat Feb 24 00:00:00 EST 2018},
month = {Sat Feb 24 00:00:00 EST 2018}
}
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Figures / Tables:
Fig. 1: Schematical representation of the concerted and stepwise methylation mechanisms with MeOH or DME as reactant.
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Works referenced in this record:
Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity
journal, April 2012
- Olsbye, Unni; Svelle, Stian; Bjørgen, Morten
- Angewandte Chemie International Edition, Vol. 51, Issue 24, p. 5810-5831
Unraveling the Reaction Mechanisms Governing Methanol-to-Olefins Catalysis by Theory and Experiment
journal, April 2013
- Hemelsoet, Karen; Van der Mynsbrugge, Jeroen; De Wispelaere, Kristof
- ChemPhysChem, Vol. 14, Issue 8
Mechanistic Aspects of the Zeolite Catalyzed Methylation of Alkenes and Aromatics with Methanol: A Review
journal, August 2011
- Svelle, Stian; Visur, Melina; Olsbye, Unni
- Topics in Catalysis, Vol. 54, Issue 13-15
Kinetics and Mechanism of Benzene, Toluene, and Xylene Methylation over H-MFI
journal, August 2013
- Hill, Ian; Malek, Andre; Bhan, Aditya
- ACS Catalysis, Vol. 3, Issue 9
Kinetics and mechanism of olefin methylation reactions on zeolites
journal, January 2012
- Hill, Ian M.; Hashimi, Saleh Al; Bhan, Aditya
- Journal of Catalysis, Vol. 285, Issue 1
Kinetics of Butene Isomer Methylation with Dimethyl Ether over Zeolite Catalysts
journal, July 2012
- Hill, Ian M.; Ng, Yong Sam; Bhan, Aditya
- ACS Catalysis, Vol. 2, Issue 8
First Principle Kinetic Studies of Zeolite-Catalyzed Methylation Reactions
journal, February 2011
- Van Speybroeck, Veronique; Van der Mynsbrugge, Jeroen; Vandichel, Matthias
- Journal of the American Chemical Society, Vol. 133, Issue 4
Quantum Chemical Modeling of Zeolite-Catalyzed Methylation Reactions: Toward Chemical Accuracy for Barriers
journal, January 2009
- Svelle, Stian; Tuma, Christian; Rozanska, Xavier
- Journal of the American Chemical Society, Vol. 131, Issue 2
Methylation of benzene by methanol: Single-site kinetics over H-ZSM-5 and H-beta zeolite catalysts
journal, August 2012
- Van der Mynsbrugge, Jeroen; Visur, Melina; Olsbye, Unni
- Journal of Catalysis, Vol. 292
Towards molecular control of elementary reactions in zeolite catalysis by advanced molecular simulations mimicking operating conditions
journal, January 2016
- De Wispelaere, Kristof; Bailleul, Simon; Van Speybroeck, Veronique
- Catalysis Science & Technology, Vol. 6, Issue 8
Complex Reaction Environments and Competing Reaction Mechanisms in Zeolite Catalysis: Insights from Advanced Molecular Dynamics
journal, May 2015
- De Wispelaere, Kristof; Ensing, Bernd; Ghysels, An
- Chemistry - A European Journal, Vol. 21, Issue 26
Benzene co-reaction with methanol and dimethyl ether over zeolite and zeotype catalysts: Evidence of parallel reaction paths to toluene and diphenylmethane
journal, May 2017
- Martinez-Espin, Juan S.; De Wispelaere, Kristof; Westgård Erichsen, Marius
- Journal of Catalysis, Vol. 349
Hydrogen Transfer versus Methylation: On the Genesis of Aromatics Formation in the Methanol-To-Hydrocarbons Reaction over H-ZSM-5
journal, August 2017
- Martínez-Espín, Juan S.; De Wispelaere, Kristof; Janssens, Ton V. W.
- ACS Catalysis, Vol. 7, Issue 9
How zeolitic acid strength and composition alter the reactivity of alkenes and aromatics towards methanol
journal, August 2015
- Westgård Erichsen, Marius; De Wispelaere, Kristof; Hemelsoet, Karen
- Journal of Catalysis, Vol. 328
New insights into catalyst deactivation and product distribution of zeolites in the methanol-to-hydrocarbons (MTH) reaction with methanol and dimethyl ether feeds
journal, January 2017
- Martinez-Espin, Juan S.; Mortén, Magnus; Janssens, Ton V. W.
- Catalysis Science & Technology, Vol. 7, Issue 13
Methanol-to-hydrocarbons conversion: The alkene methylation pathway
journal, May 2014
- Brogaard, Rasmus Y.; Henry, Reynald; Schuurman, Yves
- Journal of Catalysis, Vol. 314
Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites
journal, September 2014
- Jones, Andrew J.; Iglesia, Enrique
- Angewandte Chemie International Edition, Vol. 53, Issue 45
Reactivity Descriptors and Rate Constants for Electrophilic Aromatic Substitution: Acid Zeolite Catalyzed Methylation of Benzene and Toluene
journal, February 2002
- Vos, Ann M.; Nulens, Kim H. L.; De Proft, Frank
- The Journal of Physical Chemistry B, Vol. 106, Issue 8
Insight into the Formation and Reactivity of Framework-Bound Methoxide Species in H-ZSM-5 from Static and Dynamic Molecular Simulations
journal, June 2014
- Van der Mynsbrugge, Jeroen; Moors, Samuel L. C.; De Wispelaere, Kristof
- ChemCatChem, Vol. 6, Issue 7
Computational Assessment of the Dominant Factors Governing the Mechanism of Methanol Dehydration over H-ZSM-5 with Heterogeneous Aluminum Distribution
journal, March 2016
- Ghorbanpour, Arian; Rimer, Jeffrey D.; Grabow, Lars C.
- ACS Catalysis, Vol. 6, Issue 4
Methanol to Dimethyl Ether over ZSM-22: A Periodic Density Functional Theory Study
journal, February 2013
- Moses, Poul Georg; Nørskov, Jens K.
- ACS Catalysis, Vol. 3, Issue 4
Conversion of Methanol into Hydrocarbons over Zeolite H-ZSM-5: Ethene Formation Is Mechanistically Separated from the Formation of Higher Alkenes
journal, November 2006
- Svelle, Stian; Joensen, Finn; Nerlov, Jesper
- Journal of the American Chemical Society, Vol. 128, Issue 46
Stability and Reactivity of Intermediates of Methanol Related Reactions and C–C Bond Formation over H-ZSM-5 Acidic Catalyst: A Computational Analysis
journal, March 2016
- Wei, Zhihong; Chen, Yan-Yan; Li, Junfen
- The Journal of Physical Chemistry C, Vol. 120, Issue 11
Methane formation mechanism in the initial methanol-to-olefins process catalyzed by SAPO-34
journal, January 2016
- Wei, Zhihong; Chen, Yan-Yan; Li, Junfen
- Catalysis Science & Technology, Vol. 6, Issue 14
Understanding the Failure of Direct CC Coupling in the Zeolite-Catalyzed Methanol-to-Olefin Process
journal, March 2006
- Lesthaeghe, David; Van Speybroeck, Veronique; Marin, Guy B.
- Angewandte Chemie International Edition, Vol. 45, Issue 11
Hydrogen Transfer Pathways during Zeolite Catalyzed Methanol Conversion to Hydrocarbons
journal, November 2016
- Müller, Sebastian; Liu, Yue; Kirchberger, Felix M.
- Journal of the American Chemical Society, Vol. 138, Issue 49
Reaction Mechanisms of the Methylation of Ethene with Methanol and Dimethyl Ether over H-ZSM-5: An ONIOM Study
journal, March 2009
- Maihom, T.; Boekfa, B.; Sirijaraensre, J.
- The Journal of Physical Chemistry C, Vol. 113, Issue 16
Methylation of Alkenes and Methylbenzenes by Dimethyl Ether or Methanol on Acidic Zeolites
journal, June 2005
- Svelle, Stian; Kolboe, Stein; Swang, Ole
- The Journal of Physical Chemistry B, Vol. 109, Issue 26
Insight into the Effect of Water on the Methanol-to-Olefins Conversion in H-SAPO-34 from Molecular Simulations and in Situ Microspectroscopy
journal, February 2016
- De Wispelaere, Kristof; Wondergem, Caterina S.; Ensing, Bernd
- ACS Catalysis, Vol. 6, Issue 3
Molecular Dynamics Kinetic Study on the Zeolite-Catalyzed Benzene Methylation in ZSM-5
journal, October 2013
- Moors, Samuel L. C.; De Wispelaere, Kristof; Van der Mynsbrugge, Jeroen
- ACS Catalysis, Vol. 3, Issue 11
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends
journal, February 2015
- Medford, Andrew J.; Shi, Chuan; Hoffmann, Max J.
- Catalysis Letters, Vol. 145, Issue 3
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis
journal, August 2015
- Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S.
- Journal of Catalysis, Vol. 328
Descriptor-Based Analysis Applied to HCN Synthesis from NH3 and CH4
journal, April 2011
- Grabow, Lars C.; Studt, Felix; Abild-Pedersen, Frank
- Angewandte Chemie International Edition, Vol. 50, Issue 20
Understanding trends in C–H bond activation in heterogeneous catalysis
journal, October 2016
- Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan
- Nature Materials, Vol. 16, Issue 2
First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs
journal, January 2012
- Sabbe, Maarten K.; Reyniers, Marie-Françoise; Reuter, Karsten
- Catalysis Science & Technology, Vol. 2, Issue 10
CO Activation on Realistic Cobalt Surfaces: Kinetic Role of Hydrogen
journal, July 2017
- Banerjee, Arghya; van Bavel, Alexander P.; Kuipers, Herman P. C. E.
- ACS Catalysis, Vol. 7, Issue 8
First-Principles-Based Microkinetics Simulations of Synthesis Gas Conversion on a Stepped Rhodium Surface
journal, August 2015
- Filot, Ivo A. W.; Broos, Robin J. P.; van Rijn, Jeaphianne P. M.
- ACS Catalysis, Vol. 5, Issue 9
State-of-the-art and challenges in theoretical simulations of heterogeneous catalysis at the microscopic level
journal, January 2012
- López, Núria; Almora-Barrios, Neyvis; Carchini, Giuliano
- Catalysis Science & Technology, Vol. 2, Issue 12
Reactivity Descriptor in Solid Acid Catalysis: Predicting Turnover Frequencies for Propene Methylation in Zeotypes
journal, April 2014
- Wang, Chuan-Ming; Brogaard, Rasmus Y.; Weckhuysen, Bert M.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
Transition-state scaling relations in zeolite catalysis: influence of framework topology and acid-site reactivity
journal, January 2015
- Wang, Chuan-Ming; Brogaard, Rasmus Y.; Xie, Zai-Ku
- Catalysis Science & Technology, Vol. 5, Issue 5
Methanol–Alkene Reactions in Zeotype Acid Catalysts: Insights from a Descriptor-Based Approach and Microkinetic Modeling
journal, November 2014
- Brogaard, Rasmus Y.; Wang, Chuan-Ming; Studt, Felix
- ACS Catalysis, Vol. 4, Issue 12
First-principles kinetic Monte Carlo simulations for heterogeneous catalysis: Application to the CO oxidation at
journal, January 2006
- Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 73, Issue 4
Ab Initio Thermodynamics and First-Principles Microkinetics for Surface Catalysis
journal, January 2016
- Reuter, Karsten
- Catalysis Letters, Vol. 146, Issue 3
2D Surface Structures in Small Zeolite MFI Crystals
journal, June 2015
- Teixeira, Andrew R.; Qi, Xiaoduo; Conner, Wm. Curtis
- Chemistry of Materials, Vol. 27, Issue 13
Carbon Dioxide and Methane Transport in DDR Zeolite: Insights from Molecular Simulations into Carbon Dioxide Separations in Small Pore Zeolites
journal, June 2009
- Jee, Sang Eun; Sholl, David S.
- Journal of the American Chemical Society, Vol. 131, Issue 22
A Study of Pore Blockage in Silicalite Zeolite Using Free Energy Perturbation Calculations
journal, February 2005
- Gupta, Amit; Snurr, Randall Q.
- The Journal of Physical Chemistry B, Vol. 109, Issue 5
Modeling the occupancy dependence of diffusivities in zeolites
journal, December 2004
- Krishna, R.; Paschek, D.; Baur, R.
- Microporous and Mesoporous Materials, Vol. 76, Issue 1-3
Monte Carlo simulations in zeolites
journal, October 2001
- Smit, Berend; Krishna, R.
- Current Opinion in Solid State and Materials Science, Vol. 5, Issue 5
Ab Initio Calculation of Rate Constants for Molecule-Surface Reactions with Chemical Accuracy
journal, March 2016
- Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim
- Angewandte Chemie International Edition, Vol. 55, Issue 17
Enthalpy and Entropy Barriers Explain the Effects of Topology on the Kinetics of Zeolite-Catalyzed Reactions
journal, July 2013
- Van der Mynsbrugge, Jeroen; De Ridder, Jeroen; Hemelsoet, Karen
- Chemistry - A European Journal, Vol. 19, Issue 35
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
On the stability and nature of adsorbed pentene in Brønsted acid zeolite H-ZSM-5 at 323 K
journal, August 2016
- Hajek, J.; Van der Mynsbrugge, J.; De Wispelaere, K.
- Journal of Catalysis, Vol. 340
Physisorption and chemisorption of alkanes and alkenes in H-FAU: a combined ab initio–statistical thermodynamics study
journal, January 2009
- De Moor, Bart A.; Reyniers, Marie-Françoise; Marin, Guy B.
- Physical Chemistry Chemical Physics, Vol. 11, Issue 16
Accurate Adsorption Thermodynamics of Small Alkanes in Zeolites. Ab initio Theory and Experiment for H-Chabazite
journal, March 2015
- Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim
- The Journal of Physical Chemistry C, Vol. 119, Issue 11
Normal Mode Analysis in Zeolites: Toward an Efficient Calculation of Adsorption Entropies
journal, March 2011
- De Moor, Bart A.; Ghysels, An; Reyniers, Marie-Françoise
- Journal of Chemical Theory and Computation, Vol. 7, Issue 4
Quantum Chemical Free Energies: Structure Optimization and Vibrational Frequencies in Normal Modes
journal, October 2013
- Piccini, GiovanniMaria; Sauer, Joachim
- Journal of Chemical Theory and Computation, Vol. 9, Issue 11
Effect of Anharmonicity on Adsorption Thermodynamics
journal, May 2014
- Piccini, GiovanniMaria; Sauer, Joachim
- Journal of Chemical Theory and Computation, Vol. 10, Issue 6
Anharmonicity and Confinement in Zeolites: Structure, Spectroscopy, and Adsorption Free Energy of Ethanol in H-ZSM-5
journal, March 2016
- Alexopoulos, Konstantinos; Lee, Mal-Soon; Liu, Yue
- The Journal of Physical Chemistry C, Vol. 120, Issue 13
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, June 2009
- Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T.
- Journal of the American Chemical Society, Vol. 131, Issue 23
Kinetic studies of zeolite-catalyzed methylation reactions. Part 2. Co-reaction of [12C]propene or [12C]n-butene and [13C]methanol
journal, September 2005
- Svelle, S.; Ronning, P.; Olsbye, U.
- Journal of Catalysis, Vol. 234, Issue 2
Kinetic studies of zeolite-catalyzed methylation reactions1. Coreaction of [12C]ethene and [13C]methanol
journal, May 2004
- Svelle, Stian; Rønning, Per Ola; Kolboe, Stein
- Journal of Catalysis, Vol. 224, Issue 1
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